Continuous thermal polycondensation process for preparing polymers

ABSTRACT

A continuous process for preparing polymers is provided: The continuous process produces polymers from monoethylenically unsaturated acids or anhydrides, and a nitrogen-containing compound, optionally in the presence of a fluidizing agent. The polymers are useful as detergent additives, pigment and mineral dispersants, additives for fertilizers, and corrosion and scale inhibitors in boilers and cooling towers.

This is a divisional of application Ser. No. 08/065,848, filed May 21,1993, now U.S. Pat. No. 5,410,017.

The present invention relates to a continuous thermal polycondensationprocess for preparing polymers. In particular, the present inventionrelates to a continuous thermal polycondensation process for preparingpolypeptides. More particularly, the present invention relates to thecontinuous thermal polycondensation of ethylenically unsaturated acidsand anhydrides using ammonia, ammonium hydroxide or a primary amine.

Polypeptides, particularly polypeptides containing carboxylic acidmoieties, such as poly(aspartic acid) and those which can be hydrolysedto contain carboxylic acid moieties, such as polysuccinimides, areuseful as detergent additives, pigment and mineral dispersants,additives for fertilizers, and corrosion and scale inhibitors in boilersand cooling towers. Several processes are known for the production ofpoly(aspartic acid) and polysuccinimide. However, the known methods forthese syntheses are complex, expensive, or require excessively longprocess times. The expense of these processes may be a result of thestarting material used, the process conditions, or the recovery steps.

A method for the synthesis of poly(aspartic acid) from maleic acid andammonia is disclosed in U.S. Pat. No. 4,839,461 to Boehmke. This processis carried out by heating an aqueous solution of maleic acid or maleicanhydride, which changes into maleic acid while being heated with water,and ammonia to give a dry melt of the monoammonium to biammonium saltswhich, if the temperature is raised is converted at 120° to 150° C. intopoly(aspartic acid). Boehmke discloses that it is preferable to raisethe temperature to 125° C. to 135° C. in the course of 4-6 hours and tokeep it at this level for 0-2 hours. The maleic acid and ammonia arereacted in a molar ratio of 1:1-1.5. The mixture is then heated to120°-150° C. and the resulting solution of ammonium salt of maleic acidis evaporated, leaving a crystal mash. The crystal mash is then melted,during which time the waters of condensation and crystallization distilloff. A porous mass results. The entire process, resulting inpoly(aspartic acid) having molecular weight of from 1,000 to 4,000,requires four to eight hours to complete.

The processes for the synthesis of polypeptides, such as Boehmke'smethod for preparing polysuccinimide, are time consuming, complex,expensive, and inefficient. Other methods for preparing polypeptides,such as those using amino acids as starting materials, are also timeconsuming, complex, expensive, inefficient, generate large amounts ofwaste and frequently have the added costs and complexities of handlingsolid materials.

The present invention seeks to overcome the problems associated with theprior art.

According to a first aspect of the present invention, there is provideda continuous process for preparing polymers comprising:

(A) continuously contacting

(i) a fluid stream of one or more monomers selected from the groupconsisting of

(a) monoethylenically unsaturated acids and salts thereof, and

(b) monoethylenically unsaturated anhydrides with

(ii) a gaseous or liquid stream of a nitrogen-containing compoundselected from the group consisting of ammonia, ammonium hydroxide,primary amines and combinations thereof; and, optionally,

(iii) a fluidizing agent; to provide a reaction mixture;

(B) continuously conveying the reaction mixture through a reactor;

(C) maintaining the reaction mixture in the reactor, at a temperature offrom about 100° C. to about 300° C., to provide a residence time of fromabout 1 second to about 4 hours; and

(D) recovering a polymer product.

According to a second aspect of the present invention, there is provideda continuous process for preparing polymers comprising:

(A) continuously contacting

(i) a fluid stream of maleic anhydride or maleic acid, and optionally,one or more monomers selected from the group consisting of

(a) monoethylenically unsaturated acids, and

(b) monoethylenically unsaturated anhydrides with

(ii) a gaseous or liquid stream of a nitrogen-containing compoundselected from the group consisting of ammonia, ammonium hydroxide andcombinations thereof; and, optionally,

(iii) a fluidizing agent; to provide a reaction mixture;

(B) continuously conveying the reaction mixture through a reactor;

(C) maintaining the reaction mixture in the reactor, at a temperature offrom about 100° C. to about 300° C., to provide a residence time of fromabout 1 sec to about 4 hours; and

(D) recovering a polymer product of polysuccinimide.

The process of the present invention has the advantages of a continuousprocess, uses readily available and inexpensive starting materials, andis capable of producing solid polymer product.

One type of monomer suitable for the process of the present inventionare monoethylenically unsaturated acids. Monoethylenically unsaturatedacids can be mono-acids, di-acids or polyacids and the acids may becarboxylic acids, sulphonic acids, phosphonic acids, or salts orcombinations thereof. Preferably, the monoethylenically unsaturatedacids are carboxylic acids or salts thereof. Suitable monoethylenicallyunsaturated mono-acids are, for example, acrylic acid, methacrylic acid,crotonic acid, and the alkali metal and ammonium salts thereof. Suitablemonoethylenically unsaturated di-acids are, for example, maleic acid,cyclohexene dicarboxylic acid, itaconic acid, mesaconic acid, fumaricacid, citraconic acid, and the alkali metal and ammonium salts thereof.Preferred monoethylenically unsaturated acids are acrylic acid,methacrylic acid, maleic acid, fumaric acid and citraconic acid.

Another type of monomer suitable for the process of the presentinvention are monoethylenically unsaturated anhydrides. Suitablemonoethylenically unsaturated anhydrides are, for example, theanhydrides of cis-dicarboxylic acids, such as maleic anhydride,tetrahydrophthalic anhydride, itaconic anhydride and citraconicanhydride. The preferred monoethylenically unsaturated anhydride ismaleic anhydride.

Preferably, the one or more monomers will function as Michael-typeacceptors under the conditions of the reaction since it is believed,although the present invention is not intended to be limited thereby,that the mechanism by which the polymerization reaction proceeds is viathe Michael-type addition of one molecule into the ethylenicallyunsaturated bond of a second molecule.

The one or more monomers are used as a fluid stream. While some of thesemonomers suitable for the present invention are liquids at roomtemperature, others, such as maleic anhydride, need to be heated toachieve fluidity.

The one or more monomers are contacted with a gaseous or liquid streamof a nitrogen-containing compound selected from the group consisting ofammonia, ammonium hydroxide, primary amines and combinations thereof.Suitable primary amines include, for example, alkylamines andhydroxyalkylamines such as ethylamine, propylamine, butylamine, and thelike, ethanolamine, propanolamine, and the like. Preferably, the one ormore monomers are contacted with a gaseous or liquid stream of ammonia.The gaseous or liquid stream of the nitrogen containing compound ispreferably used at a level which provides a molar ratio of the nitrogencontaining compound to monomer of about 0.8-3:1, preferably from about0.9-1.5:1 and most preferably about 1:1.

The one or more monomers and the nitrogen-containing compound arecontacted, and are optionally contacted with a fluidizing agent. Thefluidizing agent may be a component of one or more monomer streams, orit may be a component of the nitrogen-containing compound stream, or itmay be a separate stream. Preferably, the fluidizing agent is a separatestream or is a component of the nitrogen-containing compound stream.Preferred fluidizing agents will function as a solvent, diluent, orsuspending agent for the reaction mixture. By acting as a solvent,diluent or suspending agent, the fluidizing agent may serve to: increasethe flowability of the reaction mixture as the reaction mixture proceedsthrough the reactor; increase the rate of heat transfer between thereaction mixture and the surfaces of the reactor; increase the mixingefficiency of the reaction mixture as the reaction mixture proceedsthrough the reactor; make the product easier to handle.

Preferred fluidizing agents include, for example, water, poly(alkyleneglycols), poly(alkylene oxides), surfactants and other high-boilingorganic materials such as tetrahydronaphthalene, N-methylpyrrolidinone,sulfolane, dimethyl sulfoxide, and dimethylformamide. Most preferably,the fluidizing agent is water. When water is used as the fluidizingagent, it is preferably used at a level which provides a molar ratio ofwater to monomer of up to about 3:1, more preferably about 0.5-2:1, andmost preferably about 0.75-1.3:1.

The one or more monomers, the nitrogen-containing compound, andoptionally, the fluidizing agent are preferably contacted at atemperature of from about 55° C. to about 150° C. to provide thereaction mixture. The preferred temperature of the components uponcontact may depend upon the heat transfer properties of the reactor. Forexample, if heat is being removed from the reaction mixture during thecourse of the reaction, it may be desirable to lower the temperature ofthe components upon contact. These components are preferably contactedby impinging streams of each of the components, or by introducingstreams of each of the components into a device capable of mixing thecomponents together. A suitable means for effectuating impinging streamsis by forcing the separate streams of the components through ports, ornozzles so that the components contact each other at a distance from thepods or nozzles. The pods or nozzles are preferably positioned so thatthe exiting streams impinge in the reactor, or in or near the entranceto, the reactor. It is also preferable that there be a means ofpreventing the pods or nozzles from becoming clogged or blocked.Suitable means for preventing the pods or nozzles from becoming cloggedor blocked, might be by intermittent plunging of the bore, orintermittent or continuous wiping of the tip.

After the reaction mixture is formed by contacting the one or moremonomers, the ammonia or primary amine, and optionally, the fluidizingagent, the reaction mixture is continuously conveyed through thereactor. Suitable reactors are capable of maintaining the reactionmixture at a temperature of from about 100° C. to about 300° C.,preferably from about 110° C. to about 280° C., and providing aresidence time of from about 1 second to about 4 hours, preferably fromabout 5 seconds to about 2 hours. Examples of suitable reactors aresingle or multiple screw extruders, plug-flow reactors, tube reactors,scraped-wall reactors or heat exchangers, or other continuous reactors,and combinations thereof. Preferred reactors are extruders and tubereactors equipped with static mixing elements.

The reaction which occurs between the one or more monomers and thenitrogen-containing compound may be exothermic, such as, for example,thereaction which occurs between maleic anhydride and ammonia. Thus, it ispossible to utilize this liberated heat to maintain the reaction mixtureat an elevated temperature. This would reduce, or eliminate, the demandof external heat needed to maintain the reaction mixture at atemperature of from 100° C. to about 300° C. If the temperature is toolow, it may be difficult to conduct the reaction to completion. If thetemperature is too high, some decomposition of the polymer product maybe observed. If the exotherm is too strong, it may be necessary toremove heat from the reactor during the reaction in order to maintainthe reaction mixture at a temperature of from 100° C. to about 300° C.

Preferably, the reactor is operated under an elevated pressure of atleast 1 atmosphere (atm), and most preferably at an elevated pressure offrom about 15 to about 100 atm. It may be desirable to have one or moreback-pressure control devices located along the reactor in order tomaintain a pressure of from about 15 to about 100 atm. Back-pressurecontrol devices can be used to control the temperature and pressureinside the reactor, for example, by allowing the removal of certaincomponents from the reaction mixture, such as water, ammonia, fluidizingagents, and the like.

In one embodiment of the present invention, additional components areadded to the reaction mixture. This can be accomplished, for example, byinjecting additional components into the reaction mixture at one or morepoints along the reactor. For example, it may be desirable to controlthe viscosity of the reaction mixture. This may be accomplished by theaddition of one or more of the fluidizing agents described above; or bythe addition of a thickener, or diluent. It may also be desirable to addone or more catalysts, chain extenders, or cross-linking agents. Forexample, ethanolamine, glucosamine, lysine or diamines such asethylenediamine may be added. Depending upon the intended use of theproduct, it may be desirable to add one or more components which arealso used in the formulation of the final product, for example,poly(alkylene glycols), poly(alkylene oxides), biocides, pesticides,fillers and the like.

Additional components may also be components which react with thepolymer. For example, when maleic anhydride or maleic acid is used asone of the monomers, the polymer may contain succinimide moieties.Polymers which contain succinimide moieties, such as polysuccinimide,contain units of the formula: ##STR1## in the polymer chain. Additionalcomponents can be added which would react with the polymer by reactingwith the succinimide moieties. Additional components such as bases,acids, and amines may react with succinimide moieties. Similarly, basescan be added as an additional component to neutralize any acid groups ofthe polymers.

The polymer product may be recovered in a solid or fluid form, and mayoptionally be recovered containing any fluidizing agents or otheradditional components which may have been added. It may be possible toobtain the polymer product as a pure product, for example, by reducingthe pressure of the product to volatilize any volatile componentspresent in the product stream. The polymer product may be, for example,a granular solid, flake, powder or liquid. The polymers are useful, forexample, as detergent additives, pigment and mineral dispersants,additives for fertilizers, and corrosion and scale inhibitors in boilersand cooling towers

The following examples are embodiments of the general process discussedhereinabove and are intended by way of illustration only and are notintended to limit the invention in any way. The weight average molecularweights (M_(w)) are measured by aqueous gel permeation chromatography(G.P.C.) relative to a 4,500 Mw poly(acrylic acid) standard.

Example 1

A first "T"-shaped tube (having an inner diameter of 1/16th inch and atotal volume of approximately 0.2 milliliters), equipped at one end witha means for introducing monomer into the tube and at another end with ameans for introducing ammonia into the tube, was attached via the thirdend to one end of a second "T"-shaped tube (having an inner diameter of1/16th inch and a total volume of approximately 0.2 milliliters).Another end of the second "T"-shaped tube was equipped with a means forintroducing fluidizing agent, and the third end of the "T"-shaped tubewas attached to one end of a Kenics brand static mixer (having an innerdiameter of 3/16th inch and a total volume of approximately 1.5milliliters). The other end of the static mixer was connected via a tube(having an inner diameter of 3/16th inch and a total volume ofapproximately 1.1 milliliters) to a back-pressure control device. Thestatic mixer and the tube connecting it to the back-pressure controldevice were equipped with a thermocouple, steam tracing lines andinsulation. Steam at a temperature of 140° C. was circulated through thetracing lines and the backpressure on the back-pressure control devicewas set at 250 psig. A sample of maleic anhydride was fluidized byheating to 130°-135° C., and was continuously pumped into one end of thefirst "T"-shaped tube at a rate of 11 grams/minute. The internaltemperature of the reactor was raised to about 210°-220° C. bycontinuously pumping a 30 percent by weight aqueous solution of ammoniumhydroxide into the second "T"-shaped tube at a rate of 9.0 grams/minute.The maleic anhydride was contacted with a nitrogen-containing compoundto form a reaction mixture by continuously pumping a sample of anhydrousammonia gas into another end of the first "T"-shaped tube at a rate of 2grams/minute and the ammonium hydroxide solution, acting as a fluidizingagent, was slowed to a rate of 1.9 grams/minute. At equilibrium, theresidence time was approximately 15 seconds. A tan product extruded fromthe back-pressure control device along with steam. Upon cooling theproduct hardened to a friable solid which was easily pulverized.

A sample of the product was dissolved in aqueous sodium carbonate andidentified as polysuccinimide of greater than 98% purity according toanalysis by NMR spectroscopy. The molecular weight of the polymer was1610.

Example 2

A similar procedure was followed as in Example 1 except that the staticmixer was not used and the fluidizing agent was deionized watercontinuously pumped at a rate of 2.0 grams/minute. The product waspolysuccinimide having Mw of 1140.

Example 3

A "T"-shaped tube (having an inner diameter of 1/16th inch and a totalvolume of approximately 0.2 milliliters), equipped at one end with ameans for introducing monomer into the tube and at another end with ameans for introducing ammonia into the tube, was attached to one end ofa Kenics brand static mixer (having an inner diameter of 3/16th inch anda total volume of approximately 1.5 milliliters). The other end of thestatic mixer was connected via a tube (having an inner diameter of3/16th inch and a total volume of approximately 1.1 milliliters) to aback-pressure control device. The static mixer and the tube connectingit to the back-pressure control device were equipped with athermocouple, steam tracing lines and insulation. Steam at a temperatureof 140° C. was circulated through the tracing lines and the backpressureon the back-pressure control device was set at 250 psig. A sample ofmaleic anhydride was fluidized by heating to 130°-135° C., and wascontinuously pumped into one end of the "T"-shaped tube at a rate of 11grams/minute. The internal temperature of the reactor was raised toabout 210°-220° C. by continuously pumping a 30 percent by weightaqueous solution of ammonium hydroxide into the other end of the"T"-shaped tube at a rate of 9.0 grams/minute. The aqueous ammoniumhydroxide solution was slowed to a rate of 1.8 grams per minute and wascombined with ammonia, flowing at 2.0 grams/minute, to form a stream ofnitrogen-containing compound. The maleic anhydride was contacted withthe stream of nitrogen-containing compound to form a reaction mixture bycontinuously pumping the stream of nitrogen-containing compound intoanother end of the "T"-shaped tube. At equilibrium, the residence timewas approximately 15 seconds. The product was polysuccinimide having Mwof 1710.

Example 4

A similar procedure was followed as in Example 1 except that thefluidizing agent pumped at a rate of 4.5 grams/minute. The product waspolysuccinimide having Mw of 548.

Example 5

A similar procedure was followed as in Example 1 except that thefluidizing agent was continuously pumped at a rate of 2.7 grams/minute.The product was polysuccinimide having Mw of 1780.

Example 6

A similar procedure was followed as in Example 3 except that the maleicanhydride was fluidized by heating to 115°-120° C.; the stream ofnitrogen-containing compound was formed from ammonia, flowing at 2.0grams/minute, 30 percent by weight aqueous ammonium hydroxide, flowingat a rate of 1.4 grams per minute, and 25 percent by weightethylenediamine dissolved in 30 percent by weight aqueous ammoniumhydroxide, flowing at a rate of 1.2 grams per minute. The residence timewas approximately 14 seconds. The product was polysuccinimide having Mwof 1950.

Example 7

A similar procedure was followed as in Example 3 except that the maleicanhydride was fluidized by heating to 115°-120° C.; the stream ofnitrogen-containing compound was formed from ammonia, flowing at 2.0grams/minute, 30 percent by weight aqueous ammonium hydroxide, flowingat a rate of 0.7 grams per minute, and poly(ethylene glycol) having amolecular weight of 400, flowing at a rate of 3.8 grams per minute. Theresidence time was approximately 12 seconds. The product waspolysuccinimide having Mw of 1090.

We claim:
 1. A continuous process for preparing polymers comprising:(A)continuously contacting(i) a fluid stream of one or more monomersselected from the group consisting of(a) monoethylenically unsaturatedacids and salts thereof, and (b) monoethylenically unsaturatedanhydrides with (ii) a gaseous or liquid stream of a nitrogen-containingcompound selected from the group consisting of ammonia, ammoniumhydroxide, primary amines and combinations thereof; and, optionally,(iii) a fluidizing agent; to provide a reaction mixture; (B)continuously introducing into the reaction mixture one or moreadditional components selected from the group consisting of thickeners,catalysts, acids, bases, amines, chain extenders, cross-linking agents,biocides, pesticides, and fillers; (C) continuously conveying thereaction mixture through a reactor; (D) maintaining the reaction mixturein the reactor, at a temperature of from about 100° C. to about 300° C.,to provide a residence time of from about 1 second to about 4 hours; and(E) recovering a polymer product.
 2. The process of claim 1, wherein:the monoethylenically unsaturated acids are selected from the groupconsisting of acrylic acid, methacrylic acid, crotonic acid, maleicacid, cyclohexene dicarboxylic acid, itaconic acid, mesaconic acid,fumaric acid, citraconic acid, and the alkali metal and ammonium saltsthereof.
 3. The process of claim 1, wherein: the monoethylenicallyunsaturated acids are selected from the group consisting of acrylicacid, methacrylic acid, maleic acid, fumaric acid and citraconic acid.4. The process of claim 1, wherein: the monoethylenically unsaturatedanhydrides are selected from the group consisting of maleic anhydride,tetrahydrophthalic anhydride, itaconic anhydride and citraconicanhydride.
 5. The process of claim 1, wherein: the monoethylenicallyunsaturated anhydride is maleic anhydride.
 6. The process of claim 1,wherein the molar ratio of nitrogen-containing compound to monomer isabout 0.8-3:1.
 7. The process of claim 1, wherein the molar ratio ofnitrogen-containing compound to monomer is about 0.9-5:1.
 8. The processof claim 1, wherein: the fluidizing agent is selected from the groupconsisting of water, poly(alkylene glycols), poly(alkylene oxides),surfactants, tetrahydronaphthalene, N-methylpyrrolidinone, sulfolane,dimethyl sulfoxide, and dimethylformamide.
 9. The process of claim 1,wherein: the fluidizing agent is water and the molar ratio of water tomonomer is up to about 3:1.
 10. The process of claim 1, wherein: theadditional component is a crosslinking agent selected from the groupconsisting of ethanolamine, glucosamine, lysine, and ethylenediamine.